JPH0571554B2 - - Google Patents
Info
- Publication number
- JPH0571554B2 JPH0571554B2 JP6173987A JP6173987A JPH0571554B2 JP H0571554 B2 JPH0571554 B2 JP H0571554B2 JP 6173987 A JP6173987 A JP 6173987A JP 6173987 A JP6173987 A JP 6173987A JP H0571554 B2 JPH0571554 B2 JP H0571554B2
- Authority
- JP
- Japan
- Prior art keywords
- crucible
- iridium
- phosphoric acid
- acid solution
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 35
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052741 iridium Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 9
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 7
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical group [Ir]=O YJZATOSJMRIRIW-UHFFFAOYSA-N 0.000 description 5
- 230000012010 growth Effects 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LIXXICXIKUPJBX-UHFFFAOYSA-N [Pt].[Rh].[Pt] Chemical compound [Pt].[Rh].[Pt] LIXXICXIKUPJBX-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は坩堝の洗浄方法に関し、特にガドリニ
ウムガリウム系単結晶の育成に使用したイリジウ
ム製の坩堝の洗浄方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for cleaning a crucible, and particularly to a method for cleaning an iridium crucible used for growing gadolinium gallium single crystals.
一般に、融点1700℃以上の酸化物単結晶を引上
法により育成するには通常イリジウム製の坩堝が
用いられる。高温度に加熱された状態では、イリ
ジウム製の坩堝は0.1％以上の酸素の存在で表面
が酸化され、酸化イリジウムになつて蒸発あるい
は溶解し原料中に混入する。したがつて通常、育
成は中性あるいは還元雰囲気中で行なわれている
ことが多い。
Generally, an iridium crucible is usually used to grow an oxide single crystal with a melting point of 1700° C. or higher by a pulling method. When heated to a high temperature, the surface of an iridium crucible is oxidized in the presence of 0.1% or more oxygen, becoming iridium oxide, which evaporates or dissolves and mixes into the raw material. Therefore, growth is usually carried out in a neutral or reducing atmosphere.
しかしながら、ガドリニウムガリウム系単結晶
育成の場合、中性あるいは還元雰囲気中では酸化
ガリウム（Ga2O3）が熱反応によつて著しく蒸発
し、原料の組成ずれをもたらし、あるいは酸化ガ
リウムとイリジウム金属の化学反応によつてイリ
ジウム金属を溶かし、これが原料中に混入してイ
ンクルージヨンを形成し結晶内部を歪ませ、結果
的には割れの原因になり、良好な単結晶が得られ
ないことがある。従つてやむをえず中性ガスに酸
素２％前後を混合して育成を行なつている。 However, in the case of gadolinium gallium single crystal growth, gallium oxide (Ga 2 O 3 ) evaporates significantly due to a thermal reaction in a neutral or reducing atmosphere, resulting in a compositional deviation of the raw materials, or a change in the composition of gallium oxide and iridium metal. Iridium metal is melted through a chemical reaction, which mixes into the raw material, forms inclusions, and distorts the inside of the crystal, eventually causing cracks and making it impossible to obtain a good single crystal. Therefore, it is unavoidable to mix around 2% oxygen with neutral gas for growth.
当然のことながら、坩堝内に残存した原料はイ
リジウム微粒子の混入のため２ないし３回の単結
晶育成の後全て取替えなくてはならない状態にな
る。これを簡単に行なうには、坩堝内に残存した
原料を、通常の育成のときとは逆に坩堝を上下逆
さに配置して高周波誘導加熱法等によつて融解流
出させればよい。 Naturally, the raw material remaining in the crucible must be completely replaced after two or three single crystal growths due to the contamination of fine iridium particles. To easily do this, the raw material remaining in the crucible may be melted and flowed out by high-frequency induction heating or the like by placing the crucible upside down, contrary to the normal growth.
しかしながら残存原料は流出しても、坩堝の底
部や内側壁に付着した原料残渣や酸化イリジウム
微粒子は残つてしまう。これら原料残渣や残つた
酸化イリジウム微粒子は特殊な切削工具、例えば
ダイヤモンドツールを用いて工作機械によつて取
り除かなくてはならなかつた。 However, even if the remaining raw material flows out, raw material residues and iridium oxide fine particles attached to the bottom and inner walls of the crucible remain. These raw material residues and remaining iridium oxide fine particles had to be removed by machine tools using special cutting tools, such as diamond tools.
上述した従来の坩堝の洗浄方法は、坩堝をガド
リニウムガリウム系単結晶育成の時のは上下逆に
して加熱し融解流出させた後の坩堝内の底部や側
壁面に付着している原料残渣や酸化イリジウム微
粒子を切削工具を使用して除去する構成となつて
いるので、頻繁な切削作業を必要とし、また切削
工具からの不純物の混入を招き以後育成され単結
晶の品質が阻害されるという欠点がある。本発明
の目的は、切削工具を使用しないで容易にかつ完
全に原料残渣や酸化イリジウム残渣を除去するこ
とができ、良好な単結晶を得ることができる坩堝
の洗浄方法を提供することにある。
The conventional crucible cleaning method described above involves heating the crucible upside down when growing gadolinium gallium single crystals, and then melting and draining the crucible. Since the iridium fine particles are removed using a cutting tool, frequent cutting operations are required, and the disadvantage is that impurities from the cutting tool can be mixed in and subsequently grown, impairing the quality of the single crystal. be. An object of the present invention is to provide a crucible cleaning method that can easily and completely remove raw material residues and iridium oxide residues without using cutting tools, and can obtain good single crystals.
本発明の坩堝の洗浄方法は、高周波誘導加熱引
上法によりガドリニウムガリウム系単結晶を育成
した後のイリジウム製の坩堝を加熱装置内に上下
逆さに配置して加熱し坩堝内の原料残渣、酸化イ
リジウムを含む付着物を溶解流出させた後、該坩
堝全体を150℃より高いリン酸液に浸して該坩堝
内の前記付着物を分解除去する構成を有してい
る。
In the crucible cleaning method of the present invention, after a gadolinium gallium single crystal has been grown by high-frequency induction heating pulling, an iridium crucible is placed upside down in a heating device and heated to remove raw material residue and oxidation in the crucible. After the deposits containing iridium are dissolved and flowed out, the entire crucible is immersed in a phosphoric acid solution at a temperature higher than 150° C. to decompose and remove the deposits in the crucible.
ガドリニウムガリウム系単結晶の育成後、坩堝
に固着している酸化イリジウム微粒子や原料残渣
を如何にしたら除去できるか実験事実を重ね次の
ことが判明した。
After growing a gadolinium gallium single crystal, we conducted a series of experiments to find out how to remove the iridium oxide fine particles and raw material residues stuck to the crucible, and found the following.
まず、坩堝内に付着した酸化イリジウム残渣等
を顕微鏡で調べると酸化イリジウム微粒子の結合
した部分にわずかに原料が固体状で付着してい
る。 First, when examining the iridium oxide residue etc. attached to the inside of the crucible using a microscope, it is found that a small amount of the raw material is attached in solid form to the part where the iridium oxide fine particles are bonded.
そこで酸化イリジウム微粒子と原料の固体物の
結合体を150℃の熱リン酸液に浸した結果、ほぼ
数十時間かかつてこれらは分解した。 Therefore, when the combination of iridium oxide particles and the solid raw material was immersed in a hot phosphoric acid solution at 150°C, they decomposed in approximately several tens of hours.
このリン酸液は温度が高くなるほど分解率が増
し、約350℃では数時間以内で坩堝内に付着した
酸化イリジウム残渣等は完全に分解除去できるこ
とが判明した。 The decomposition rate of this phosphoric acid solution increases as the temperature rises, and it was found that at approximately 350°C, iridium oxide residues etc. attached to the crucible could be completely decomposed and removed within several hours.
そこで本発明はこの事実を根拠に、坩堝を150
℃より高いリン酸液に浸し酸化イリジウム残渣等
を除去するようにした。 Based on this fact, the present invention has developed a crucible of 150
The iridium oxide residue was removed by immersing it in a phosphoric acid solution at a temperature higher than ℃.
次に、本発明の実施例について図面を参照して
説明する。
Next, embodiments of the present invention will be described with reference to the drawings.
第１図は本発明の一実施例を説明するための洗
浄装置及び坩堝の断面図ある。 FIG. 1 is a sectional view of a cleaning device and a crucible for explaining one embodiment of the present invention.
まず、高周波誘導加熱引上法によつてガドリニ
ウムガリウム系単結晶を育成した後のイリジウム
製の坩堝を、加熱炉装置１の中に上下逆にして配
置して加熱し坩堝内の原料残渣、酸化イリジウム
残渣等の付着物を融解流出させる。 First, an iridium crucible after growing a gadolinium gallium single crystal by high-frequency induction heating pulling method is placed upside down in the heating furnace device 1 and heated to remove raw material residue and oxidation in the crucible. The deposits such as iridium residue are melted and flowed out.
次に、第１図に示すように加熱炉装置１内にリ
ン酸液３を入れた白金ビーカー２を入れ、リン酸
液３中に坩堝４全体を浸して加熱、坩堝４に付着
した原料残渣、酸化イリジウム残渣等を分解除去
する。 Next, as shown in FIG. 1, a platinum beaker 2 containing a phosphoric acid solution 3 is placed in the heating furnace device 1, and the entire crucible 4 is immersed in the phosphoric acid solution 3 and heated, thereby removing the raw material residue attached to the crucible 4. , iridium oxide residue, etc. are decomposed and removed.
この後、坩堝４には付着したリン酸液は温水に
より除去する。 Thereafter, the phosphoric acid solution adhering to the crucible 4 is removed with warm water.
次に、本発明を実施したときの結果について説
明する。 Next, the results obtained when implementing the present invention will be explained.
イリジウム製の坩堝４には、内径50mm深さ50mm
板厚1.5mmでGd3Ga4Al1O12の単結晶育成を３回行
い、原料中の酸化イリジウム微粒子が多くなりイ
リジウムインクルージヨンの発生で育成した単結
晶に割れが起きたため原料を取替えることになつ
た坩堝を使用した。 Iridium crucible 4 has an inner diameter of 50 mm and a depth of 50 mm.
We grew a single crystal of Gd 3 Ga 4 Al 1 O 12 three times with a plate thickness of 1.5 mm, and the number of iridium oxide fine particles in the raw material increased, causing cracks in the grown single crystal due to the generation of iridium inclusions, so we had to change the raw material. I used an old crucible.
まず、この坩堝４を逆さにして加熱し付着物を
融解流出させた後、坩堝４を白金ビーカー２（内
径100mm深さ100mm板厚0.7mm）中に入れリン酸液
３が坩堝全体に浸るように630c.c.入れた。 First, this crucible 4 is heated upside down to melt and drain the deposits, and then the crucible 4 is placed in a platinum beaker 2 (inner diameter 100 mm depth 100 mm plate thickness 0.7 mm) so that the entire crucible is immersed in the phosphoric acid solution 3. I put 630c.c. into it.
そしてこれらを加熱炉装置１に入れヒーター１
１に電力600Wを加えた。リン酸液の温度測定は
白金−白金ロジウム13％の熱電対５を液の中間に
入れて行つた。 Then, put these into the heating furnace device 1 and the heater 1
1 plus 600W of power. The temperature of the phosphoric acid solution was measured by placing a platinum-platinum rhodium 13% thermocouple 5 in the middle of the solution.
リン酸液３を360℃に２時間保持した結果坩堝
４内に付着していた酸化イリジウム微粒子等は完
全に分解除去することができた。 As a result of holding the phosphoric acid solution 3 at 360° C. for 2 hours, the iridium oxide fine particles adhering to the inside of the crucible 4 could be completely decomposed and removed.
この後、温水によりリン酸液を除去し、再び
Gd3Ga4Al1O12の単結晶を育成したところ、割れ
もなく良好な品質の単結晶が得られた。 After this, remove the phosphoric acid solution with warm water and re-
When a single crystal of Gd 3 Ga 4 Al 1 O 12 was grown, a single crystal of good quality with no cracks was obtained.
なお、リン酸液３の温度管理は比較的むずかし
いが、熱電対５からの温度情報によりヒーター１
１の電力を制御しリン酸液３の温度を制御するこ
とができる温度調節部を設けることにより、容易
にかつ再現性よくリン酸液３の温度管理をするこ
とができる。 Although it is relatively difficult to control the temperature of the phosphoric acid solution 3, the temperature information from the thermocouple 5 allows the heater 1 to
By providing a temperature control section that can control the power of the phosphoric acid solution 1 and the temperature of the phosphoric acid solution 3, the temperature of the phosphoric acid solution 3 can be easily controlled with good reproducibility.
以上説明したように本発明は、坩堝全体を150
℃より高い温度のリン酸液に浸して坩堝内の付着
物を分解除去する構成とすることにより、従来必
要とした切削工具による頻繁な切削作業が不要と
なるので、切削工具からの不純物の混入がなく、
しかも容易にかつ完全に付着物を除去することが
でき、良好な単結晶を得ることができる効果があ
る。
As explained above, the present invention allows the entire crucible to be heated to 150
By immersing the crucible in a phosphoric acid solution at a temperature higher than ℃ to decompose and remove deposits inside the crucible, frequent cutting operations using cutting tools, which were previously required, are no longer necessary, thereby eliminating the contamination of impurities from cutting tools. There is no
In addition, it is possible to easily and completely remove deposits and obtain good single crystals.
第１図は本発明の一実施例を説明するための洗
浄装置及び坩堝の断面図である。
１……加熱炉装置、２……白金ビーカー、３…
…リン酸液、４……坩堝、５……熱電対、１１…
…ヒーター。
FIG. 1 is a sectional view of a cleaning device and a crucible for explaining one embodiment of the present invention. 1... Heating furnace device, 2... Platinum beaker, 3...
...Phosphoric acid solution, 4... Crucible, 5... Thermocouple, 11...
…heater.
Claims (1)
リウム系単結晶を育成した後のイリジウム製の坩
堝を加熱装置内に上下逆さに配置して加熱し坩堝
内の原料残渣、酸化イリジウムを含む付着物を融
解流出させた後、該坩堝全体を150℃より高いリ
ン酸液に浸して該坩堝内の前記付着物を分解除去
することを特徴とする坩堝の洗浄方法。1 After growing a gadolinium gallium single crystal using the high-frequency induction heating pulling method, the iridium crucible is placed upside down in a heating device and heated to melt and flow out the raw material residue and deposits containing iridium oxide in the crucible. A method for cleaning a crucible, which comprises immersing the entire crucible in a phosphoric acid solution at a temperature higher than 150° C. to decompose and remove the deposits inside the crucible.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6173987A JPS63230589A (en) | 1987-03-16 | 1987-03-16 | Cleaning of crucible |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6173987A JPS63230589A (en) | 1987-03-16 | 1987-03-16 | Cleaning of crucible |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63230589A JPS63230589A (en) | 1988-09-27 |
| JPH0571554B2 true JPH0571554B2 (en) | 1993-10-07 |
Family
ID=13179860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6173987A Granted JPS63230589A (en) | 1987-03-16 | 1987-03-16 | Cleaning of crucible |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63230589A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102430552A (en) * | 2011-11-28 | 2012-05-02 | 天通控股股份有限公司 | Cleaning method for crucible for crystal growth |
| CN109092783B (en) * | 2018-08-14 | 2021-08-27 | 信阳师范学院 | Method for cleaning ceramic crucible |
| CN112513347B (en) * | 2019-08-21 | 2021-12-24 | 眉山博雅新材料股份有限公司 | Crystal with neutron and gamma/X ray detection functions and preparation method thereof |
| CN114130753A (en) * | 2021-11-24 | 2022-03-04 | 枣庄睿诺电子科技有限公司 | Process method for removing organic material residues in crucible |
-
1987
- 1987-03-16 JP JP6173987A patent/JPS63230589A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63230589A (en) | 1988-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69932760T2 (en) | Method and apparatus for producing a silicon rod having a structure produced by directional solidification | |
| DE102017206741A1 (en) | Apparatus and method for producing a gallium oxide crystal | |
| Chevy | Improvement of growth parameters for Bridgman-grown InSe crystals | |
| JPH0571554B2 (en) | ||
| JPS6345198A (en) | Production of crystal of multiple system | |
| JP5794955B2 (en) | Method for manufacturing substrate with β-Ga2O3 single crystal film | |
| JPH035392A (en) | Production device of silicon single crystal | |
| Kouta et al. | β-BaB2O4 phase-matching-direction growth by the Czochralski method | |
| JPH0653634B2 (en) | Regeneration method of quartz crucible for pulling silicon single crystal | |
| JPS60191094A (en) | Pretreatment of bn crucible | |
| DE3002671C2 (en) | Process for making a silicon carbide substrate | |
| JP2712594B2 (en) | Method for producing group 3-5 compound semiconductor single crystal | |
| EP0760024B1 (en) | Process and device for obtaining unfissured crystals | |
| JP7163762B2 (en) | Method for evaluating grain boundaries of iron-gallium alloy crystals | |
| JP5040812B2 (en) | Method for removing substance solidified in crucible and crucible regeneration method | |
| JPS6212692A (en) | Method for growing single crystal semiconductor | |
| JP2806624B2 (en) | Noble metal crucible and crystal manufacturing method | |
| JP2934121B2 (en) | Single crystal manufacturing method | |
| Linz et al. | Growth of fluoride laser host crystals | |
| JPS6230698A (en) | Growth of single crystal | |
| JPS60180989A (en) | Manufacture of compound single crystal | |
| EP0725978A1 (en) | Quartz glass jig for the heat treatment of silicon wafers and method and device for producing same | |
| WO2006064882A1 (en) | Process for producing boric acid compound crystal and boric acid compound crystal produced by said process | |
| JPS62119198A (en) | Device for rotating and pulling up single crystal provided with magnetic field impressing device | |
| JPH07187898A (en) | Production of oxide single crystal |